Bis(cyanoalkyl) phenylenedicarbamates



' 3,036,112 BIS(CYANOALKYL) Pl-IENYLENEDIC K John W. Lynn, Charleston, W. Va, assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed Sept. 15, 1959, Ser. No. 839,990 4 Claims. (Cl. 260-465) This invention relates to bis(cyanoalkyl) phenylenedicarbamates as new compositions of matter, and to processes for their production.

The novel bis(cyanoalkyl) phenylenedicarbamates of this invention can be graphically depicted by the formula:

wherein R is a divalent saturated hydrocarbon radical containing from 1 to 10 carbon atoms, such as methylene, ethylene, propylene, isopropylene, decylene, cyclohexylene-and the like, and R R R and R are members selected from the group consisting of hydrogen and lower alkyl radicals. 1 By the term lower alkyl as used herein is meant an alkyl radical having from 1 to 6 carbon atoms, inclusively. Illustrative examples of the novel bis(cyanoalkyl) phenylenedicarbamates of this invention include bis(2-cyanoethyl) 4-methyl-1,3-phenylenedicarbamate which can be represented by the formula:

11111- O-OCH2-OH2-CN NH000,0H20Hz-0N and such compounds as: Bis(l-cyanoethyl) 4-methyl-1,3-phenylenedicarbamate Bis(2-cya noisopropyl) 4 methyl 1,3 phenylenedicarbamate 'Bis(2-cyanoethyl) 4-ethyl-1,3-phenylenedicarbamate Bis(1-cyanoethyl) -isopropyl-1,3 phenylenedicarbamate Bis(1-cyanoethyl) 1,3-phenylenedicarbamate Bis( l-cyanomethyl) 4-methy1-1,3-phenylenedicarbamate Bis(1-cyanomethyl) 4-hexyl-1,3-phenylenedicambamate Bis'( l-cyanomethyl) 1,3-phenylenedicarbamate Bis(2-cyanocyclohexyl) 4 methyl 1,3 phenylenedicarbamate Bis(2-cyanocyclohexyl) 1,3-phenylenedicarbamate Bis(cyanomethyl) 4,6-diisopropyl 1,3 phenylenedicarbamate Bis(2-'cyanodecy-l) 4-methyl 1,3 phenylenedicarbamate and the like.

The bis(cyanoalkyl) phenylenedicarbamates of this invention can be produced by the reaction of a phenylene- 'diisocyanate compound with a cyanohydrin compound.

The phenylenediisocyanate compounds which can; be employed as starting materials in preparing the novel compounds of this invention can be graphically depicted by the formula:

ITTCO NCO wherein R R R and R are as above defined. Illus- 3,@3fi,112 Patented Mayaz, 1962 ice '2 trative of such starting materials is 4-methyl-1, 3-pheny1- enediisocyanate which can be represented by the formula:

' NCO and such compounds as 4-ethyl-1,3phenylenediisocyanate, 5-isopropyl 1,3-phenylenediisocyanate, 1,3-phenylenediisocyanate, 4-hexyl-1,3-phenylenediisocyanate, 4,6-diisoprowl- 1,3phenylenediisocyanate, and the like.

The cyanohydrin compounds which can be employed as starting materials in preparing the novel compounds of this invention can be graphically depicted by the-formula:

wherein R is as above defined. Illustrative of such starting materials is ethylene cyanohydrin which can be represented by the formula:

HO-CH -CHQ-CN and acetone cyanohydrin which can be represented by the formula:

wherein R, R R R and R are as above defined. Thus, for example, bis(2-cyanoethyl) 4-methyl41,3-phenylenedicarbamate can be prepared by the reaction of 4-methy1- 1,3-phenylenediisocyanate with ethylene cyanohydrin', and bis(2-cyanoisoprop-y1-2-yl) 4-methyl-1,3 phenylenedicarbamate can be prepared by the reaction of 4-methyl-1,3- phenylenediisocyana-te with acetone cyanohydrin.

When efiecting reaction according to the process of the instant invention, it is preferable to employ an excess of cyanohydrin compound over the stoichiometric amount required to react with the phenylenediisocyanate compound present in order to ensure complete conversion of the phenylenediisocyanate compound. Amounts of cyanohydrin compound ranging from the stoichiometric equivalent to a 3 :1 mole ratio are prefer-red'for this purpose, but amounts of from as little as 1 mole to as much as 20 moles per mole of phenylenediisocyanate compo n Pres nt an l be e l yed Reaction be wee a ph hr h sh yah h rqh and a cyanohydrin compound according to the process of the instant invention is promoted by and preferably effected in the presence of a catalyst. Specific examples 1 10 the precipitate obtained thereby was slurred in about 200 of the catalysts which can be employed include tertiary amines such as pyridine, trimethylamine, triethylamine, tri n propylamine, triisopropylamiue, tributylamine, methyldiethylamine, dimethylethylamine, benzyldimethylamine, benzyldiethylamine, ethylenediamine and the like, .dialkyltin oxides such as d'ibutyltin 'oxide, diisopropyltin oxide, dioctyltin oxide, and the like, and di-v .allgyltlrt diacylates such as dibutyltin dia'cetate, di-' propyltindipropionate, dibutyltin benzoate and the like.

"The catalyst can be employed in an amount of from as low as 0.001 percent by weight to as high as 1 percent by weight, preferably from 0.01 percent by weight to 0.05 percent by weight, of the combined weight of reactants employed. 7

Rea t on accor n to h Pro of e i n h- 'tion readily occurs at temperatures ranging from as low 25 as C. to as high as150 C., but is preferably efiected at temperatures ranging from iabout20 C. to about 60 C. Atmospheric pressure is usually employed in effecting reaction according to the process of the instant invention. However, pressure both above and below atmospheric pressure, for example pressures ranging from as low as 100 mm. Hg to as highas 1000 p.s.i., can also be employed whenever it is desirable to do so.

Reaction according to the process of the instant invention may be effected in an inert liquid solvent. By an inert liqu d. o ve is m an a l i solvent in which the starting materials are soluble to an extent whereby they are brought into reactive contact and which itself is nonreactive under the conditions of the reaction. Suit- .able inert liquid solvents which can be employed include hy req rb n u h a xane rc oh e heptane, benzene, toluene and the like, and ethers such as dioxane,

tetrahydrofuran and the like. 'In general, an amount of solvent ranging from 0 to times,'preferably from '0 to 2 times, the weight :of reactants present can be effectively employed. i V r V The novel bis(cyanoalkyl) phenylenedicarbamates of this invention are useful as soil fungicides and herbicides. The following examples areset forth for purposes of illustration so that those skilled in the art may better understand this invention, and 'it should be understood that they are not to be construed as limiting'this invention in any manner.

1 .EXAMPLE I Preparation of Bis(2-Cyanoethyl) 4-Methyl-1,3-

Phenylitedicarbamate An admixture of 87 grams of 4-methyl-l,3-phenylenediisocyanate (0.5 mole), 71 grams of ethylene cyanohydrin (1.0 mole), 0.5 mi. ofpyridine, and 500 ml. of benzcn'e was prepared and maintained 'at room temperature wfor' J16 lholurs; The mixture :was then filtered and the precip'itate obtained thereby was crystallized trn'e' ofacetonitri'le and petroleum ether. About 155 bis(2 -cyauoethyl-) '4-methyl-1,3rphenylenedi- V carbamate were recovered. represented a 'yieldgof frornie grams of about .98 percent of th'eoretical. Thisoicompound had a melting point of l25l27 C. and was identified by its infrared absorption spectrum andchemiical analysis.

Analysis.Caleulated for c grr gmo C, {57.1%;1H, 5.06%,"N, 17.7%. Fo'undz C, 58. 1%; H, 4.91 N, 1 .3%. r z 7 4 EXAMPLE 11 Preparation of Bis(1-Cyanoethyl) 4-Methyl-1,3-

Phenylenedicarbamate ml. of diethyl ether and then separated therefrom by filtration. About 31 grams of bi s(1 -eyauoethyl) 4-methyl- 1,}phenylenedicarbamate were obtained in this manner. This represented a yield of about 3 9v percent of theoret- 15 ical, This compound, which deeornposed at a te mpera- 3 tered and the ture of 115430." C., was identified by its infrared absorption spectrum and chemical analysis. V

Analysis.-Calculated for C H N O C, 57.1%; H,

5.06%; N, 17.7%. Found: C, 58.5%; H, 5.5%; N,

EXAMPLE III Preparation of Bis(2-Cyanoisopropy'l) 4-Methyl-I,3- Phenylenedicarbamate An admixture of 43.5 grams of 4-methyl-l,3-phenylenediis ocyanate (0.25 mole), 43 grams of acetone cyanohydrin (0.5 mole), 0.2 gram of dibutyltin oxide, and 400 ml. of benzene was prepared and maintained at room temperature fgr40, hours. The mixture was then filx precipitate obtained thereby was washed with benzene. About 59; grams of bis(2-cyanoisoproyl) ;4 methyl-1,3-phenylenedicarbamate was obtained in this manner, This represented a yield of about 69 percent "of theoretieal. This compound had a melting point of 3 125-127 C. and was identified by its infrared absorption spectrum and chemical analysis.

Analysis-Calculated for C H N O C, 59.5%; H, 5.81%; N, 16.27%. Found: C, 59.4%; H, 5.9%; N, 16.13%.

EXAMPLE IV Use of Bis(2-Cyanoi.ropropyl) 4 -Methyi-L3- Bhenylenedicarbamate as a Soil Fungicide The test soil employed in this experiment was artificially infestedvwith Rhyzqct oniq .solani (sore-shin of cot 1cm) fungus. The soil was prepared by culturing the fungus on 40 grams of No. 1 Hard Red Winter Wheat suspended-in m1. of distilledwater for about 15 days at 70 1? and then. incorporating the fungus-infested wheat suspension into an amount of sterile soil equal to 50 the volume of ten 4-in9h pots by means of a cement mixer. The wheat employed in culturing the fungus was previously autocl-aved with 50 ml. of distilled water in a .125 ml; Erlenmeyer .flask f9r:3.0 minutes at 15 lb. pressure, and then shaken to form a loose mass.

FORE-41111911 pots were filled with test soil prepared in accordance with the, above pro edure. After lightly watering the soil, the pots were stored in an incubation shamhermaih h hhd t a t pe t 0M5 and 1 relative humidity for 2 days." At the end of this time,

ml. of a test emulsion containing bis(2'-cyanoisopropyl)4-inethyl l,3 phenylenedicarban1ate' was added to eachof two of the" clay pots. :The emulsion employed was prepared by dissolving 0.25 gram of. the bis(2-cyanoisopropyl') t methyl-lfi phenylenedicarbamate in 1.0 ml. 5 of acetone, adding 0.025 ml. of 'Tergitol'Nonionic NPX -'(-an alkyl phenyl ether of polyethylene glycol, sold commereially. by Union Carbide Corporation, New York, New York) as an emulsifier, and. then diluting the mixture up to ml. with water. A similar emulsion free from -bis(2-cyanoisopropyl 4 -rnethyl-1,3-phenylenedicarbamate was added to the other. two pots which are employed as controls.

' j The pots were incubated at room temperature for two .75 days. At the end of this time, each pot was seeded with 15 seeds of Coker 100 cotton seed and stored in the greenhouse. After 15 days had elapsed, the pots were examined and it was found that 70.89 percent of the seedlings in the pots that had been treated with the emulsion containing bis(2-cyanoisopropyl) 4-methyl-1,3- phenylenedicarbamate had germinated while only 0.24 percent of the seedlings in the control pots had germinated.

EXAMPLE V Use of Bis(Z-Cyanaisopropyl) 4-Methyl-1,3-Phenylene- Dicarbamate as a Herbicide A mixture of 31 ml. of Setaria iralz'ca var. stramineofructa (Golden Millet) seeds, 12 ml. of Amaranthus retroflexus (Red Root) seeds, and 6100 ml. of sifted soil was prepared and rolled on a ball mill in a two-gallon container for approximately one-half hours (in order to insure uniform mixing of seeds and soil). Seventy (70) ml. of this mixture were then added to each of three 3- inch clay pots that had been previously filled with soil to about 1 /2 inches from their tops. After tamping the seed-soil mixture firmly, the pots were removed to a greenhouse and lightly watered. About two hours later, 25 ml. of a test emulsion containing bis (2-cyanoisopropy1) 4-methyl-1,3-phenylenedicarbamate was added to each of two of the clay pots. The emulsion employed was prepared by dissolving 0.25 gram of the bis(2-cyanoisopropyl) 4-methyl-1,3-phenylenedicarbamate in ml. of acetone, adding 0.025 ml. of Tergitol Nonionic NPX (an alkyl phenyl ether of polyethylene glycol, sold commercially by Union Carbide Corporation, New York, New York) as an emulsifier, and then diluting the mixture up to 100 ml. With water. A similar emulsion free from bis(2-cyanoisopropyl) 4-methyl-1,3-phenylenedicarbamate was addeed to the third pot which was employed as a control.

The pots were stored in a greenhouse and lightly watered for three weeks. At the end of this time, the pots were examined and it was found that the Setaria italica var. stramineofructa and Amaranthus retroflexus species that had been treated with bis(2-cyanoisopropyl) 4-n1ethyl-1,3-phenylenedicarbamate were stunted and/0r reduced in stand as compared to the species in the control pot.

Unless otherwise specified, all parts and percentages, as used throughout this specification, are by weight.

What is claimed is:

1. The bis(cyanoalkyl) phenylenedicarbamates represented by the general formula:

References Cited in the file of this patent UNITED STATES PATENTS 2,789,128 Tursich Apr. 16, 1957 2,789,129 Bissinger Apr. 16, 1957 2,798,885 Ensslin et a1. July 9, 1957 OTHER REFERENCES Saunders et al.: Chem. Revs. 43, 209-210 (1948). Migrdichion, The Chemistry of Organic Cyanogen Compounds, 1947, page 383, 

1. THE BIS(CYANOALKYL) PHENYLENEDICARBAMATES REPRESENTED BY THE GENERAL FORMULA: 